Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 11
Showing 1-50 articles out of 69 articles from the selected issue
  • Tohru Azumi, Hiroshi Azumi
    1966 Volume 39 Issue 11 Pages 2317-2320
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The radiative lifetimes of the excimer fluorescence of naphthalene are calculated for excimers of various geometrical configurations. The results vary, to a great extent, with the configurations, but with a previously-suggested configuration the calculated lifetime is 6×10−6 sec. This is within a factor of 5 of the experimental results.
  • Kichisuke Nishimoto, Ryoichi Fujishiro, Shuzo Akiyama, Masazumi Nakaga ...
    1966 Volume 39 Issue 11 Pages 2320-2322
    Published: 1966
    Released: March 27, 2006
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    The electronic spectra of 1,1′-dianthrylpoly-ynes have been studied by Hückel MO theory on the basis on various approximations for resonance integrals. A good agreement between theoretical and experimental values is obtained from a modified bond-alternation approximation. This result shows that the contribution of a cumulene-type ionic structure to the ground state of the molecule increases with an increase in the number of the triple bonds.
  • Hirotaka Shimanouchi, Tamaichi Ashida, Yoshio Sasada, Masao Kakudo, Ic ...
    1966 Volume 39 Issue 11 Pages 2322-2331
    Published: 1966
    Released: March 27, 2006
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    Crystals of 8, 8-dicyanoheptafulvene, C10H6N2, are monoclinic, with two molecules in a unit cell with the dimensions a=7.84, b=13.14, c=3.99 Å, and β=97.9°; the space group is P21m. The intensities were recorded on multiple-film equi-inclination Weissenberg photographs and measured visually against a standard scale. A trial structure was constructed from the Patterson projections, P(u, v) and P(u, w), and a Harker section, P(u, 1/2, w). The atomic coordinates and anisotropic temperature factors were refined by the least-squares method. The final R factor for (hkl) reflections is 0.107. A considerable bond alternation in the conjugated seven-membered ring has been observed. The average long and short bond lengths in the ring are 1.44 and 1.34 Å respectively. The shortest C=C bond measures 1.31 Å, which is shorter than that in ethylene. The exocyclic C=C bond length is 1.42 Å, suggesting a considerable dipolar resonance structure, one which may be responsible for the stability of the compound. The C≡N bond length is 1.13 Å. The molecule deviates slightly from being planar; it lies nearly parallel to the (101) plane. All the intermolecular separations correspond to normal van der Waals interactions; the perpendicular distance between the molecular planes is 3.4Å. The thermal motion was interpreted in terms of rigid body vibrations, and the bond lengths and angles were corrected for the rotational oscillations.
  • Koji Shigehara
    1966 Volume 39 Issue 11 Pages 2332-2335
    Published: 1966
    Released: March 27, 2006
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    The sound velocity (U) and the density of aqueous solutions of sodium dodecyl (SDS) and octyl (SOS) sulfates with inorganic electrolyte have been measured by using a differential ultrasonic interferometer and a float balance respectively, and the compressibility (β) has then been calculated from these results. The CMC’s of SDS solutions of various concentrations of sodium salts have been determined from U-vs.-SDS and β-vs.-SDS concentration (C2) diagrams. The results show a linear relationship between the logarithm of CMC and the logarithm of the concentration of sodium ions. The values of dβ⁄dC2 below CMC are affected by the addition of electrolytes, while the values above CMC are almost not affected at all by the addition of electrolytes. The diagrams of dβ⁄dC2 of alkyl sulfate vs. the number of carbon atoms in alkyl sulfate molecules with varying concentrations of added electrolytes showed straight lines which all passed through the same point when extrapolated to a zero number of carbon atoms. These results have been explained by taking account of the dissolved state of a surface active substance under the builder action of added inorganic electrolytes, which action decreases not only the mutual repulsion of the ionized-head group of a surface active substance but also the non-ionic hydration of the CH2-chain of the surface active substance.
  • Hiroshi Sato
    1966 Volume 39 Issue 11 Pages 2335-2340
    Published: 1966
    Released: March 27, 2006
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    Polyurethanes were prepared from polycaprolactone, 4, 4′-diphenylmethane diisocyanate, and ethylene diamine. Two kinds of polymers were used for the present experiments. One contained polycaprolactone with the number-average molecular weight, \barMn, of 1.30×103, while the other contained polycaprolactone with an \barMn value of 2.80×103. Each polymer was fractionated from a dimethyl acetamide solution by progressive precipitation with a mixture of n-heptane and ethyl ether, and the fractions were characterized in terms of viscosity and sedimentation. The relations between the intrinsic viscosity and the molecular weight were found in DMF at 25°C to be:
    [η]=5.52×10−4M0.66
    for the polymer containing polycaprolactone (\barMn=1.30×103) and
    [η]=7.71×10−4M0.62
    for the polymer containing polycaprolactone (\barMn=2.80×103). The viscosities of the solutions of the polymers were measured in several solvents at different temperatures, and the polymer-solvent interaction parameters were obtained by using the Fixman theory for the expansion factor. The molecular-weight distribution of the polymer containing polycaprolactone (\barMn=1.30×103) was obtained from the distribution of the sedimentation coefficient, while the value of \barMw⁄\barMn was calculated from the distribution curve to be 1.95.
  • Hiroshi Sato
    1966 Volume 39 Issue 11 Pages 2340-2344
    Published: 1966
    Released: March 27, 2006
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    Linear and branched polyurethanes, both of which contained polycaprolactone (\barMn=1.80×103), were prepared. Each polymer was fractionated from a dimethyl acetamide solution by precipitation with a mixture of n-heptane and ethyl ether, and the fractions were characterized by viscosity and sedimentation. The degree of branching for the fractions of the branched polymer was estimated by using the relation between viscosity and branching, derived by Flory. The ratio of the concentration dependence of the sedimentation coefficient ks to [η] was about 1.7 for the linear polymer, but the ks⁄[η] value increased with an increase in the degree of branching for the branched polymer. The Huggins constant, k′, seems to be independent of the degree of branching.
  • Tetsuo Miyazaki, Shoji Shida
    1966 Volume 39 Issue 11 Pages 2344-2346
    Published: 1966
    Released: March 27, 2006
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    The yields and reactions of t-C4H9+ produced in the radiolysis of neopentane in the gas phase have been studied by the use of ammonia. The yields of iso-C4H8 increase sharply upon the addition of a small amount of ammonia in the radiolysis of neopentane and show a constant value upon the further addition of ammonia (more than 10 mol.%). Since this increase is due to the following reaction:
    t−C4H9++NH3→ iso−C4H8+NH4+
    we get G(t-C4H9+)=1.76 by assuming the increment of iso-C4H8 to be equal to the yield of t-C4H9+. This value is consistent with the value expected from the mass spectrum of neopentane. It has, therefore, been concluded that the ammonia method is a very effective general method for studying the reactions of ions. It is applicable to the study of ions under high pressures, ions which can not be studied by a mass spectrometer. It is especially effective in the study of less reactive ions.
  • Teijiro Yonezawa, Isao Morishima
    1966 Volume 39 Issue 11 Pages 2346-2351
    Published: 1966
    Released: March 27, 2006
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    The chemical shifts for N,N-disubstituted amides and some other isoelectronic compounds as pure liquid and in dilute solutions in CCl4 are reported. The characteristic shifts generally observed on going from a CCl4 solution to pure liquid are explained in terms of specific self-association in the pure liquid.
  • Tetsu Takeyama, Hajime Miyama
    1966 Volume 39 Issue 11 Pages 2352-2355
    Published: 1966
    Released: March 27, 2006
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    An investigation was made of ammonia oxidation in shock waves at temperatures from 2100 to 2600°K by monitoring the ultraviolet absorption of ammonia at 2245 Å. The absorption coefficient of ammonia was measured at various temperatures; the rate constant of the decomposition reaction at higher temperatures with a mixture of 1% NH3 and 99% Ar was found to be in good agreement with the results of other studies. By using several mixtures of ammonia and oxygen highly diluted with argon, the rate of ammonia consumption immediately after an induction period was found to be expressed by:
    −\left(\fracd[NH3]dt\ ight)0=k0[NH3]1.5[O2]0.5[Ar]0.5
    where: logk0(11.5mole−1.5sec−1)=12.77±0.10+(−8488±573)⁄T. This corresponds to an apparent activation energy of 38.8±2.6 kcal./mole.
  • Shizuo Fujiwara, Yuzuru Fujiwara, Makoto Nagai
    1966 Volume 39 Issue 11 Pages 2356-2361
    Published: 1966
    Released: March 27, 2006
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    Molecular interactions between oxygen and organic molecules are investigated in detail. It was confirmed that the broadening of spectral lines due to oxygen is appreciable only with hydroxyl protons. This effect is attributed to the enhancement of the proton exchange of OH groups by oxygen. Detailed investigation was made with methanol-oxygen system. In relation with this, a new method is proposed which makes the measurement of heat of dissolution of oxygen in methanol possible.
  • Yuzuru Hiragi, Sukeji Kachi, Toshio Takada, Norihiko Nakanishi
    1966 Volume 39 Issue 11 Pages 2361-2364
    Published: 1966
    Released: March 27, 2006
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    An electron diffraction study was done with fine aragonite particles about 0.5 to 1.0 μ in size. The specimens were obtained by mixing a boiled calcium chloride solution (0.1 N) with 0.1 N of an ammonium carbonate solution. Extra spots were observed with half-integer indices {1⁄2,1⁄2,l}. This suggests the existence of a structure that differs from that of normal aragonite. From an X-ray diffraction study of the specimen, a {1/2, 3/2, 0} diffraction was also observed. The structure for explaining these half-integer diffractions is presented as a superstructure of aragonite; it belongs to the space group of D2h15Pbca, with cell dimensions of A=8.420 Å, B=9.385 Å, and C=5.741 Å, and it containes 8 formula units in a unit cell. A dark-image photograph shows this anomalous area to be comparatively wide and suggests that the anomalous area is dominant in a crystal. The authors conclude that rapidly-precipitated aragonite powders contain a small quantity of the repeatedly-twinned crystals mentioned above.
  • Hiroshi Toyuki, Kazuhiro Shimizu
    1966 Volume 39 Issue 11 Pages 2364-2368
    Published: 1966
    Released: March 27, 2006
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    A normal coordinate treatment has been carried out on the basis of the Urey-Bradley force field in order to obtain a set of the most probable assignments and the transferable force constants for the sulfuryl fluoride, the chloride and the fluorochloride series. The assignments selected and the force constants obtained have been satisfactory. The potential energy distributions have been calculated and the vibrational modes have been estimated for each molecule.
  • Takaji Takigawa, Tamaichi Ashida, Yoshio Sasada, Masao Kakudo
    1966 Volume 39 Issue 11 Pages 2369-2378
    Published: 1966
    Released: March 27, 2006
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    The hydrochloride and hydrobromide of L-tryptophan crystallize in the monoclinic space group P21. The cell dimensions of the hydrochloride are: a=7.45, b=5.30, c=14.67 Å, β=98.80°, and those of the hydrobromide are: a=7.64, b=5.41, c=14.58 Å, β=100.47°. There are two molecules in the unit cell. The two compounds are isomorphous. The crystal structure of the hydrobromide was first determined by the heavy atom method with two-dimensional data, and then that of the hydrochloride was refined by three-dimensional least-squares procedure. The molecular and crystal structure is mainly discussed for the hydrochloride here. The average of six C–C bond lengths in the benzene ring is 1.396 Å, that of C–N bond lengths in the indole ring is 1.384 Å. In the carboxyl group, one C–O bond length, 1.147 Å and two O–C–C angles, 106.8° and 125.7° are significantly different from those reported for amino and carboxyl acids so far investigated. The molecule consists of two planes of the carboxyl group and of the indole ring, the planes making an angle of 70.6° with each other. As to the conformation about the C(α)–C(β) bond, C(γ) lies at the gauche position with both of the carboxyl and the amino groups. The molecules are arranged in double layers parallel to the ab plane; the polar layer is held together by a network of the three N–H··· Cl hydrogen bonds, 3.17, 3.19 and 3.24 Å and one O–H···C1, 3.04 Å, and in the non-polar layer, the indole rings are packed mainly by van der Waals forces, the shortest C···C and C···N contacts being 3.74 and 3.42 Å respectively.
  • Hisashi Odani, Shigeru Kida, Mikio Tamura
    1966 Volume 39 Issue 11 Pages 2378-2385
    Published: 1966
    Released: March 27, 2006
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    Absorption and desorption of benzene and ethyl acetate by atactic polystyrene (A-PS) were studied at various temperatures below the glass transition point of the polymer. In the A-PS+ benzene system raising temperature did not alter the general feature of the family of successive differential absorption curves, but merely compressed the whole family of curves towards a low concentration region. The critical concentration of penetrant at which the transition from non-Fickian to Fickian behavior occurred became lower in the order benzene, ethyl methyl ketone, and ethyl acetate. The logarithm of the time, t*, which specifies the inflection point of the second stage on the two-stage absorption curve, were linearly dependent on the initial concentration of penetrant, Ci, and the correlation lines between log t* and Ci obtained for various combinations of temperature and solvent were nearly parallel with one another. The features of integral absorptions were essentially the same in all cases, and the absorption curves showed a pronounced dependence on concentration.
  • Hiroshi Shimizu
    1966 Volume 39 Issue 11 Pages 2385-2395
    Published: 1966
    Released: March 27, 2006
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    The non-Debye reorientation processes in which the Debye equation is inapplicable are studied for spherical molecules by using an equation proposed by the author. The physical meaning of the angular correlation in the non-Debye processes is discussed in detail. It is shown that in the non-Debye processes the non-dissipative decay of the mutual-phase correlation of rotating molecules must be taken into account, in addition to the dissipative decay due to molecular collisions, and that the use of the “microscopic viscosity” in the Debye equation is not plausible. It is also shown that, in contrast to the Debye processes, there is no one-to-one correspondence between the correlation time for molecular reorienation and the mean life time of the rotation, since the contribution from the nondissipative decay should be considered also. The vector and the tensor correlation functions,
    ⟨cosθ(0)cosθ(t)⟩ and ⟨(1⁄2){3cos2θ(0)−1}{(1⁄2)3cos2θ(t)−1}⟩,
    and the corresponding spectral densities, the band shapes of infrared and Raman spectra respectively, are obtained theoretically for various conditions and are shown graphically. As illustravtie examples of the treatment, methane and deutero methane molecules are studied. Vector correlation functions are obtained from the observed band shapes of the infrared spectra of these molecules. Comparing the theoretical correlation functions with experimental ones, it is shown that a reasonable agreement between theory and experiment is obtained and that methane molecules have a typical non-Debye reorientation process even below the freezing point. Some characteristic features of the non-Debye process are also discussed.
  • Shiro Ueda, Mitsuyasu Tada
    1966 Volume 39 Issue 11 Pages 2395-2399
    Published: 1966
    Released: March 27, 2006
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    Alkyl ammonium polyphosphate (AAPP) was prepared readily by a thermal reaction of alkyl (ethyl, n-propyl, n-butyl) dihydrogen phosphate and urea at temperatures ranging from 120°C to 200°C. At the same time, a small amount of cyanuric acid was obtained as a by-product. 1) AAPP was confirmed, from a study of the data of infrared spectroscopy, paper chromato-graphy and chemical analysis, to have a long-chain structure possessing P–O–P linkage. The three types of AAPP were of almost the same form, according to the X-ray diffraction patterns. 2) AAPP was more or less hygroscopic, although the hygroscopicity of AAPP decreased with an increase in the carbon number of the alkyl group. 3) AAPP is reasonably stable, keeping a P–O–P linkage even upon degradation in an acidic aqueous solution.
  • Takeshi Ando, Keihei Ueno
    1966 Volume 39 Issue 11 Pages 2400-2405
    Published: 1966
    Released: March 27, 2006
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    The oximes of aminoacetone-N, N-diacetic acid, ω-aminoacetophenone-N, N-diacetic acid, p-bromo-ω-aminoacetophenone-N, N-diacetic acid and 2-glycylthiophene-N, N-diacetic acid have been synthesized as the colorimetric reagents for iron(III). The most favourable result was obtained with the oxime of ω-aminoacetophenone-N, N-diacetic acid, which forms a stable orange red chelate with iron(III), showing an absorption maximum at 420 mμ. With the use of this reagent, 0–25 p. p. m. of iron(III) can be determined at pH 5.5. It should be noticed that this reagent is almost specific for iron (III); serious interferences were only observed for copper (II), vanadate, fluoride and phosphate ions.
  • Masumi Koishi
    1966 Volume 39 Issue 11 Pages 2406-2410
    Published: 1966
    Released: March 27, 2006
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    The hydration processes of calcium orthoplumbate are studied by means of a twin-type conduction calorimeter. The curves of the differential electromotive force vs. the hydration time have two characteristic maxima, corresponding to two exothermic processes: the first one is due to the immersion and dissolution of calcium orthoplumbate, while the second one is caused by the formation of crystalline hydrates. The heat liberated by the first process is about 1.14 cal./g. Ca2PbO4, while that liberated by the second process is about 52.22 cal./g. Ca2PbO4. The reaction in the second process proceeds by the 2/3 order; this may be explained by assuming that the rate of the reaction is determined by the surface area of the calcium orthoplumbate being hydrated.
  • Yoshihiko Mizutani, Tsutomu Sugiura
    1966 Volume 39 Issue 11 Pages 2411-2414
    Published: 1966
    Released: March 27, 2006
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    The stability of native sulfur in solfataras depends upon the temperature, the pressure, and the chemical composition of the solfataric gases with which native sulfur is in equilibrium. The equilibrium constant of the 2H2S+SO2=3S(s,1)+2H2O reaction may be expressed as:
    K=\fracX2H2OX2H2SXSO2P,
    where X is the mole fraction of the gaseous components in the system and where P is the total pressure on the system. By the use of this relationship, the equilibrium temperature of natural solfataric gases with respect to the reaction may be estimated, provided the theoretical value of K, the chemical composition, and the pressure of natural solfataric gases are known. The attainment of chemical equilibrium of the reaction in solfataric gases of the Nasudake Volcano has been examined by comparing the estimated equilibrium temperature with the observed outlet temperature of the solfataras. The results indicate that the native sulfur occurring in the solfataras is approximately in equilibrium with the solfataric gases. On this basis, an attempt has also been made to explain the behavior of hydrogen sulfide and sulfur dioxide in solfataric gases.
  • Sigeo Kida
    1966 Volume 39 Issue 11 Pages 2415-2417
    Published: 1966
    Released: March 27, 2006
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    Potassium tetrachloro(ethylenediamine)iridate(III) and cis-dichlorobis(ethylenediamine) iridium(III) chloride were obtained by the reaction of iridium(III) chloride and ethylenediamine in a weakly acid aqueous solution. The condition for the formation of each compound depends on the mole ratio of iridium to ethylenediamine and pH of the solution. Trans-dichlorobis(ethylenediamine)iridium(III)chloride was prepared from potassium tetrachloro(ethylenediamine)iridate(III) and ethylenediamine.
    The geometrical configurations of the two isomers were determined by infrared spectra, and checked by ultraviolet spectra.
  • Takaji Yasui, Jinsai Hidaka, Yoichi Shimura
    1966 Volume 39 Issue 11 Pages 2417-2424
    Published: 1966
    Released: March 27, 2006
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    In order to study the vicinal effect of the L-amino acid coordinated in a complex on the central metal ion, a number of cobalt(III) L-amino acid complexes of three types were prepared, i. e., [Co(NH3)5(L-amH)]X3, [Co(L-am)(NH3)4]SO4, and trans-[Co en2(L-amH)2]X3, where L-amH denotes an L-amino acid, and where X is Cl, Br, or I. The circular dichroism (CD) and the rotatory dispersion (RD) spectra of their aqueous solutions were measured in the wavelength range from 650 to 300 mμ. In the region of the first absorption band, both the [Co(NH3)5(L-amH)]3+ and the trans-[Co en2(L-amH)2]3+ ions show one or two CD bands to be expected in complexes of the C4v symmetry with a structure of the [Co N5O]-type and of the D4h symmetry with a structure of the trans-[Co N4O2]-type respectively. The positions of the CD bands observed in the trans complexes coincide well with the maxima of the split components, Ia and Ib, of the first absorption band. The CD spectra of different [Co(L-am)(NH3)4]2+ ions, in which L-am is a bidentate ligand, show a variety of behavior; they are discussed from a stereochemical point of view. An intense CD band of the [Co(L-prol)(NH3)4]2+ ion at about 510 mμ can be attributed to the vicinal effect of an asymmetric nitrogen atom of the coordinated L-prolinate ion. For the trans-[Co en2(L-amH)2]X3 complexes, the rotatory parameters and rotatory strengths were calculated by means of analyses of the experimental CD and RD curves.
  • Akira Misono, Yasuzo Uchida, Masanobu Hidai, Yoshiro Ohsawa
    1966 Volume 39 Issue 11 Pages 2425-2429
    Published: 1966
    Released: March 27, 2006
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    The reaction of isoprene by the catalyst systems composed of cobalt(III) or iron(III) ace-tylacetonate, an electron donor, and triethylaluminum was studied. It was found that isoprene is selectively dimerized to form a mixture of 1,5- and 2,5-dimethyl-1,5-cyclooctadiene by the catalyst prepared by the reaction of iron(III) acetylacetonate, 2,2′-dipyridyl, and triethylaluminum. The intermediate complex of the reaction was then examined by studying the effects of the molar ratio of the catalyst components on the reaction or by the measurement of the electronic absorption spectra of the reaction solution. The reaction of butadiene with the catalyst systems described above was also carried out and compared with that of isoprene.
  • Yoshinobu Takegami, Chikao Yokokawa, Yoshihisa Watanabe
    1966 Volume 39 Issue 11 Pages 2430-2433
    Published: 1966
    Released: March 27, 2006
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    The ratio between the α- and β-carbethoxypropionaldehyde formed in the oxo reaction of ethyl acrylate is affected by various reaction conditions; the proportion of β-carbethoxypropionaldehyde increases with an increase in the reaction temperature, but decreases with an increase in the partial pressure of carbon monoxide or hydrogen. These effects can be explained on the basis of the reaction mechanism between cobalt hydrocarbonyl and ethyl acrylate (Y. Takegami et al., This Bulletin, 37, 1190 (1964)): in the first step of the reaction, ethyl acrylate reacts with cobalt hydrocarbonyl to give, selectively, α-carbethoxypropionylcobalt carbonyl (I), and then I isomerizes to β-carbethoxypropionylcobalt carbonyl (II). Accordingly, the rates of two competitive reactions, the isomerization of I to II and the reduction of I to the corresponding aldehyde, may be the factors determining the distribution of the oxo reaction products. Under the oxo reaction conditions, the isomerization of I to II seems to occur more easily at a relatively high temperature and to be prohibited by a high pressure of carbon monoxide. On the other hand, a relatively high pressure of hydrogen seems to be favorable to the reduction of I to the aldehyde.
  • Atsuo Nagasawa, Hisao Kitano, Kenichi Fukui
    1966 Volume 39 Issue 11 Pages 2434-2437
    Published: 1966
    Released: March 27, 2006
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    The reaction of n-butyl or s-butyl bromide with potassium cyanate in dimethylformamide was carried out at 100°C for 3 hr. to give tri-n-butyl or tri-s-butyl isocyanurate. In this process, the presence of unpolymerized n-butyl or s-butyl isocyanate in the reaction mixture was detected by treating the mixture with benzylamine, thus forming 1-n-butyl or 1-s-butyl-3-benzyl urea. The presence of 1-butanol in the reaction system resulted in an increase in the yield of the corresponding isocyanurates. This tendency was remarkable when s-butyl bromide was used as a starting material. The addition of n-butyl N-n-butyl- or n-butyl N-s-butylcarbamate to the reaction system strongly accelerated the formation of isocyanurates. The acceleration due to the addition of 1-butanol described above was, therefore, attributed to the effect of carbamates formed in the reaction system. An attempt to trimerize n-butyl or s-butyl isocyanate in the presence of carbamates and dimethylthylformamide, or in the presence of carbamates and potassium cyanate, resulted in failure. Therefore, carbamates acted as strong accelerators for the trimerization of butyl isocyanates, in cooperation with basic alkali metal salts, such as potassium cyanate, in dimethylformamide.
  • Yoshiro Ogata, Yasuji Izawa, Takao Tsuda, Katsuhiko Takagi
    1966 Volume 39 Issue 11 Pages 2438-2441
    Published: 1966
    Released: March 27, 2006
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    The photochemical sulfoxidation of alkylbenzenes with sulfur dioxide and oxygen in acetic anhydride to give the corresponding sulfonic acids has been studied. The sulfoxidation of the higher alkylbenzenes, such as that with a side-chain of trimerized propylene (ABTP) with a total average mol. wt. of 253 and that with a linear side-chain (ABL) with an average mol. wt. of 254, and also that of ethylbenzene give, by homolytic reaction, the corresponding sulfonic acids substituted at their side-chains. In contrast, the sulfonation of m-xylene occurs at the benzene ring by ionic reaction, while toluene gives a very poor yield of sulfonic acid. The surface activities of the resulting sodium alkylbenzenesulfonate with their sulfonate group at the side-chain were comparable to the corresponding ring-substituted sulfonates.
  • Shigeru Oae, Teruya Kashiwagi, Seizi Kozuka
    1966 Volume 39 Issue 11 Pages 2441-2443
    Published: 1966
    Released: March 27, 2006
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    The Hunsdiecker reaction of optically active silver β-phenylisobutyrate with bromine was carried out, and racemic β-phenylisopropyl bromide and optically atcive 3-methyl-7-bromo-hydrocoumarin were obtained as the major products. Meanwhile, the Simonini reaction was also performed with the same optically active acid and iodine; 1-phenyl-2-propyl β-phenylisobutyrate was obtained as the product here. Upon the hydrolysis of the ester, the resulting alcohol, β-phenylisopropyl alcohol, was found to be racemic. From these observations, the mechanisms involving the formation of the incipient free radical during the reactions were suggested for both the reactions.
  • Yoshio Kitahara, Kozo Doi, Tadahiro Kato
    1966 Volume 39 Issue 11 Pages 2444-2449
    Published: 1966
    Released: March 27, 2006
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    Methoxyl groups of alkyl-2,3-dimethoxy-8,8-dicyanoheptafulvenes were easily replaced by various kinds of nucleophilic reagents to give the corresponding substituted-8,8-dicyanoheptafulvenes. There exists a difference in reactivity between the two methoxyl groups located at the 2 and 3 positions of 8,8-dicyanoheptafulvenes. The isopropyl group at the 4 position of 2,3-dimethoxy-8,8-dicyanoheptafulvene hindered some substitution reactions of the methoxyl group at the 3 position.
  • Tadahiro Kato
    1966 Volume 39 Issue 11 Pages 2450-2453
    Published: 1966
    Released: March 27, 2006
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    2,3-Diamino and 2,3-bismethylamino-8,8-dicyanoheptafulvenes gave the corresponding crystalline salts of hydrochloride. From the infrared and ultraviolet spectra, it was concluded that these hydrochlorides are the derivatives of the hydrochloride of 2-aminotropoimine.
  • Nobuo Mori, Yojiro Tsuzuki
    1966 Volume 39 Issue 11 Pages 2454-2458
    Published: 1966
    Released: March 27, 2006
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    The preferential direction of intramolecular hydrogen bonding in isomeric hydroxycyclohexyl-carbinols in dilute carbon tetrachloride solutions has been investigated by infrared spectroscopy. The 1-hydroxy isomer contains a tertiary hydroxyl group predominantly bonded to the oxygen atom of a primary hydroxyl, while the cis- and trans-2-hydroxy isomers contain a primary hydroxyl group mainly bonded to the oxygen atom of a secondary hydroxyl; the other isomers are internally unbonded. On the other hand, bis-hydroxymethyl-cyclohexanes other than the 1,1- and 1,2-isomers are unbonded. These findings can be explained in terms of the acidity of the hydroxyl groups and the steric effect on the orientation of the groups.
  • Akira Misono, Yasuzo Uchida, Kunikazu Yamada
    1966 Volume 39 Issue 11 Pages 2458-2463
    Published: 1966
    Released: March 27, 2006
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    Low-pressure copolymerization was carried out in a water-methanol mixture (1 : 1 by weight) at 0°C. It was found that, when hydroperoxides were used as cocatalysts, triethylboron and tri-rc-butylboron were active as catalysts, while triphenylboron was inactive. As cocatalysts,, hydroperoxides were more active than disubstituted peroxides. The highest catalytic activity was observed when the cocatalyst/catalyst molar ratio was 0.4. The initiating radical has been suggested to be the hydroxy radical, and the initiating mechanism has been discussed briefly. The yield and the reduced specific viscosity of the copolymer decrease rapidly with an increase in the ethylene content of the monomer mixture. The monomer reactivity ratios were: r1(vinyl chloride) = 4.16 and r2(ethylene) = 0.05. This indicates that the copolymerization reaction proceeds via a normal radical mechanism. The resulting copolymer shows characteristic absorption peaks at 750 cm−1 in the infrared spectrum and at 8.37 τ in the NMR spectrum.
  • Yasuo Shigemitsu, Tamotsu Tominaga, Takashi Shimodaira, Yoshinobu Odai ...
    1966 Volume 39 Issue 11 Pages 2463-2466
    Published: 1966
    Released: March 27, 2006
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    The direct introduction of an ethoxycarbonyl group by the photolysis of various substituted formates (RCO2C2H5) was carried out. Both ethyl cyanoformate and ethyl chloroformate effectively underwent ethoxycarbonylation by a hydrogen-donating solvent such as cyclohexane, with the yields of 19% and 15%, respectively. On the other hand, the photolysis of ethyl acetate, diethyl carbonate, and ethyl carbamate gives mainly carbinols and carbon monoxide instead of ethyl carboxylate. On the basis of these results, the effects of the substituent in the formate on the ethoxycarbonylation were considered. First, the electronic effect of the substituent R has an influence on the position of the bond fission of the formate. Cyano and chloro groups, which are the electron-withdrawing substituents, weaken the R-carbon bond in the formates. Second, the ability of the hydrogen abstraction of the radical R produced by the photolysis of the formate is very important in the ethoxycarbonylation. Thus, it is clear that there is a relationship between the electron affinity of the radical R and the yield of the ethyl carboxylate.
  • Shigeo Nishimura, Michiko Hama
    1966 Volume 39 Issue 11 Pages 2467-2470
    Published: 1966
    Released: March 27, 2006
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    The rate of the hydrogenation of benzyl alcohol with a rhodium catalyst decreases markedly in the course of the reaction, accompanied by the formation of an increasing amount of cyclohexanecarboxaldehyde with the conversion of the alcohol. The decrease in the rate is only slight with a platinum catalyst, however, and the formation of the aldehyde is much less than with the rhodium catalyst. It has been shown that cyclohexanecarboxaldehyde is an effective catalyst poison in the hydrogenation of benzyl alcohol, but that cyclohexylcarbinol is not. 1-Cyclohexenylcarbinol, an intermediate of the hydrogenation, isomerizes to cyclohexanecarboxaldehyde during the hydrogenation on rhodium and 7 : 3 rhodium-platinum catalysts to a greater extent than on the platinum catalyst. Cyclohexanecarboxaldehyde is hydrogenated only very slowly, but the rate with the platinum catalyst is about four times greater than that with the rhodium catalyst. These results may account for the different behaviors of the rhodium or 7 : 3 rhodium-platinum catalyst and the platinum catalyst observed in the hydrogenation of benzyl alcohol.
  • Noboru Sugiyama, Choji Kashima, Yoshitaka Hosoi, Tsuneo Ikeda, Ryotaro ...
    1966 Volume 39 Issue 11 Pages 2470-2473
    Published: 1966
    Released: March 27, 2006
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    Altenin, a metabolite of Alternaria Kikuchiana Tanaka, produces the black spot disease on the leaves and fruits of the pear. The optimum conditions for a 200-1. tank culture of this fungus will be described. Altenin has been tentatively deduced as being an ethyl ester of a C7-carboxylic acid. Of the four expected tautomeric structures, the probability of a furanose ring structure will be demonstrated. There is only one asymmetric center in altenin, at the position α to the ethoxycarbonyl group; this belongs to the L-lactic acid configuration.
  • Hiroshi Watanabe, Shigeru Kuwata, Tatsuo Sakata, Keizo Matsumura
    1966 Volume 39 Issue 11 Pages 2473-2476
    Published: 1966
    Released: March 27, 2006
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    DL-β-(4-Thiazolyl)-α-alanine has been synthesized in a good yield by the condensation of 4-thiazolylmethyl chloride and diethyl acetamidomalonate, and by the subsequent hydrolysis of the product. The N-carbobenzoxy derivative of this amino acid could be prepared easily and transformed to its p-nitrophenyl ester and t-butoxycarbonylhydrazide, but it was found difficult to obtain the methyl ester or the benzyl ester directly from this amino acid. Carbobenzoxy-DL-β-(4-thiazolyl)-α-alanyl-glycine benzyl ester has been synthesized by several coupling methods: its yield decreased in the following order: p-nitrophenyl ester>dicyclohexylcarbodiimide (glycine ester was used as a free base)>dicyclohexylcarbodiimide (glycine ester p-toluenesul-fonate was used without triethylamine)>dicyclohexylcarbodiimide (glycine ester p-toluenesulfonate was used with triethylamine)>mixed anhydride. The alkaline hydrolysis of the protected di-peptide ester afforded the N-protected peptide in a good yield. Decarbobenzoxylation did not proceed smoothly by catalytic hydrogenation, in which hydrogen was absorbed slowly and incompletely, while it proceeded normally with hydrobromic acid in acetic acid.
  • Otohiko Tsuge, Masashi Tashiro
    1966 Volume 39 Issue 11 Pages 2477-2479
    Published: 1966
    Released: March 27, 2006
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    In order to elucidate the chemical structure of red crystals (A) obtained from the reaction of acenaphthenequinone (I) with ammonia, the reaction of I with ammonia, formamide or benzylamine was reinvestigated. It has been made clear again that the compound A is not acenaphthazine (II) but acenaphtho[l, 2-b]isoimidazole-2-spiro-2′-acenaphthenone (III), and that Schonberg’s assumption of the structure of the compound A is incorrect. That reaction of I with benzylamine afforded II as yellow needles in a good yield. Also, it has been found that the reaction product (B) of I with formamide is a mixture of almost equal amounts of II and III.
  • Tetsuro Miki, Toshinobu Higashimura, Seizo Okamura
    1966 Volume 39 Issue 11 Pages 2480-2485
    Published: 1966
    Released: March 27, 2006
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    The initiation mechanism in the cationic polymerization of trioxane by the BF3 coordination complex catalyst was studied in ethylene dichloride at 30°C. The coordination complexes of BF3 with diethyl ether (Et2O), ethyl alcohol (EtOH) and acetic acid (AcOH) were used as catalysts. Under similar conditions, the rates of polymerization decreased in the order: BF3·EtOH>BF3·AcOH>BF3·Et2O, whereas the molecular weights of the polymers decreased in the order: BF3·Et2O>BF3·EtOH\simeqBF3·AcOH. The molecular weight of the polymer formed was unaffected by the addition of the same compound as the donor molecule in the BF3 coordination complex. However, on the addition of EtOH to the polymerization system catalyzed by BF3·Et2O, the rate of polymerization increased and the molecular weight of the polymer decreased. On the other hand, the addition of Et2O to the system catalyzed by BF3·EtOH decreased the rate of polymerization and increased the molecular weight of the polymer formed. The order of catalytic reactivity and the effect of the additive support the idea that the initiation reaction, is not an interaction of the BF3 molecule with trioxane but an addition of the cation produced from the BF3 coordination complex to the trioxane molecule.
  • Yoshio Iwakura, Shin-ichi Izawa, Fusakazu Hayano
    1966 Volume 39 Issue 11 Pages 2485-2489
    Published: 1966
    Released: March 27, 2006
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    N-Acylethylurethans reacted with phenyl glycidyl ether to produce 3-acyl-5-phenoxymethyl-2-oxazolidones, 5-phenoxymethyl-2-oxazolidone and N-(2-acyloxy-3-phenoxypropyl)ethylurethans. The reaction mechanism involving acyl migration was discussed.
  • Yoshio Iwakura, Shin-ichi Izawa
    1966 Volume 39 Issue 11 Pages 2490-2494
    Published: 1966
    Released: March 27, 2006
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    The reaction between acid amides and aryl glycidyl ethers was carried out using tertiary amine as the catalyst. 2-Oxazolidone derivatives were obtained by the reaction of trichloroacetanilide or trifluoroacetanilide with aryl glycidyl ether. Acyl migration occurred in the reaction of acetanilide with phenyl glycidyl ether.
  • Kenichi Murata, Akira Terada
    1966 Volume 39 Issue 11 Pages 2494-2499
    Published: 1966
    Released: March 27, 2006
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    1-Phthalimido-1,3-butadiene (1-PB) and 1-succinimido-1,3-butadiene (1-SB) were co-polymerized readily with acrylonitrile, methyl methacrylate and styrene, but somewhat less readily with vinyl acetate. The monomer reactivity ratios for the system with styrene were calculated by the Fineman-Ross method and found to be r1(1-PB)=1.48, r2(St)=0.32 for the 1-phthalimido-1,3-butadiene-styrene system, and r1(1-SB)=1.62, r2(St)=0.28 for the 1-succinimido-1,3-butadiene-styrene system. The Q, e-values for these systems were successively evaluated and obtained as Q (1-PB)=1.57, e(1-PB)=+0.06, Q (1-SB)=1.76 and e(1-SB)=+0.09, when Q (St)=1.0 and e(St)=−0.8. Likewise, such values for N-vinyl phthalimide (VPI) and N-vinyl succinimide (VSI) were investigated in order to compare them with the values obtained above for the imidobutadienes; they were shown to be r1(VPI)=0.09 and r2(St)=6.3 for the N-vinyl phthalimide-styrene system, and r1(VSI)=0.07 and r2(St)=9.6 for the N-vinyl succinimide-styrene system. Subsequently, the following Q and e values were determined: Q (VPI)=0.09, e(VPI)=−0.13, Q(VSI)=0.06, and e(VSI)=−0.17.
  • Yoshiro Ogata, Takashi Morimoto
    1966 Volume 39 Issue 11 Pages 2500-2502
    Published: 1966
    Released: March 27, 2006
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    The effects of alcohols, carbonyl compounds and dimethyl sulfoxide on the pyridine-cuprous chloride-catalyzed autoxidation of o-cresol in benzene have been studied kinetically by estimating the consumption of oxygen. The rate is first-order in the concentration of o-cresol and one-half order in the partial pressure of oxygen at constant concentrations of pyridine and cuprous chloride in a solvent of methanol-benzene (20 : 80 in vol.). The reaction in a benzene solution is retarded by the addition of below 0.1 vol.%, methanol or ethanol; having passed through a minimum at ca. 0.1 vol.%, it is accelerated by the addition of alcohol more than 0.1 vol.%. The reaction in a benzene solution is retarded by the addition of carbonyl compounds. A probable mechanism which explains these solvent effects is discussed.
  • Tadashi Masamune, Kazuhiko Orito, Akio Murai
    1966 Volume 39 Issue 11 Pages 2503-2508
    Published: 1966
    Released: March 27, 2006
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    N-Acetyl-22, 27-iminojerva-5, 12-diene-3β, 23α-diol-11-one, prepared from jervine by Masamune et al. (J. Org. Chem., 29, 2282 (1964)), was submitted to a Birch reduction and then to a modified Wolff-Kishner reduction to yield 22, 27-iminojerv-5-ene-3β, 23α-diol. The compound was then degraded, according to the procedure by Johnson et al. (Tetrahedron Letters, 1963, 545), to a methyl ketone, which was then further oxidized by the Oppenauer method to give 17α-ethyletiojerv-4-ene-3, 20-dione.
  • Etsuro Kurosawa, Motowo Izawa, Koji Yamamoto, Tadashi Masamune, Toshi ...
    1966 Volume 39 Issue 11 Pages 2509-2512
    Published: 1966
    Released: March 27, 2006
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    The structures of new sesquiterpenes, dictyopterol and dictyopterone, isolated from the essential oil of a brown algae, Dictyopteris divaricata Okamura (“Yezoyahazu”), have been shown to be selinen-1β-ol and selinen-1-one, respectively, on the basis of chemical and spectral data. Dictyopterol is an inseparable mixture of α- and β-isomers.
  • Hiroshi Minato, Ryuki Hisada, Mitsugu Tanaka
    1966 Volume 39 Issue 11 Pages 2512-2516
    Published: 1966
    Released: March 27, 2006
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    ω, ω′-Dibenzoylcarbohydrazide (DBC) was oxidized with sodium hypochlorite in an aqueous ethanolic solution at −70°C. At first the solution had a deep red color, but it gradually faded away. The products of the reaction isolated were benzoic acid, ethyl benzoate, carbon dioxide, 2-phenyl-1, 3, 4-oxadiazol-5-one, and N,N′-dibenzoylhydrazine. Then, DBG was oxidized with hypochlorous acid, the products of this reaction were not very different from those obtained with sodium hypochlorite. A plausible mechanism was presented, which assumed the formation of bis(benzoylimino)urea, which was then decomposed heterolytically by the nucleophilic attack of ethanol and water molecules.
  • Masatoshi Sugiyama, Mitsuo Masaki, Masaki Ohta
    1966 Volume 39 Issue 11 Pages 2517-2520
    Published: 1966
    Released: March 27, 2006
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    1-Chloro-2-oximino-3-butanone (I) was prepared by the nitrosation of chloroethyl methyl ketone with an alkyl nitrite. I was treated with the L-leucine ethyl ester (II) to give 2-(2-oximino-3-oxobutylamino)-4-methylvalerate (III) and 2-[N, N-bis(2-oximino-3-oxobutyl)amino]-4-methyl-valerate (IV). In a similar manner, l-bromo-3-oximino-2-butanone (V) was treated with II to give 2-(3-oximino-2-oxobutylamino)-4-methylvalerate (VI). The reaction of the carbonyl group of III and VI with hydroxylamine and hydrazine was also studied. The treatment of VI with ammonia gave 6-(2-oximinoethyl)-3-isobutyl-2-hydroxypyrazine. Reactions of I and V with other esters of amino acids were also carried out.
  • Akira Terada
    1966 Volume 39 Issue 11 Pages 2520-2522
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    3-Chloromethyl-4-chloro-1,2-diphenylbutan-2-ol was obtained by a Grignard reaction of 2-benzoyl-1,3-dichloropropane using benzyl chloride, which was turned into 2-benzyl-2-phenyl-3-chloromethyl-trimethylene oxide by the alkali dehydrochlorination. Heating this oxide with an excess of piperidine at 170°C for 22 hr. gave 2-benzyl-2-phenyl-3-piperidinomethyl-trimethylene oxide and a small amount of 1,2-diphenyl-3-piperidinomethyl-2,4-butanediol. The same procedures with morpholine gave 2-benzyl-2-phenyl-3-morpholinomethyl-trimethylene oxide; with ethanolic dimethyl amine, however,afforded only 1,2-diphenyl-3-dimethylamino-methyl-2,4-butanediol.
  • Yoshihide Kotera, Tadao Sekine, Masao Takahashi
    1966 Volume 39 Issue 11 Pages 2523-2526
    Published: 1966
    Released: March 27, 2006
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    The activators in the zinc sulfide phosphors were analyzed by colorimetry. The reagents were p-dimethylaminobenzylidene-rhodanine for the determination of silver in zinc sulfide and sodium dithiocarbamate, and zinc dibenzyldithiocarbamate for copper. The analytical procedures were discussed, and the range of the activator content to which these procedures are applicable was clarified. The methods were then used to determine the activator contents in the phosphors in the form of powder and single crystals; the results obtained make it clear that the activators are dissipated during the firing process in the preparation of phosphors and that copper is incorporated during the single-crystal preparation.
  • Etsuro Echigoya, Hiroshi Hagiwara, Akio Sakurai
    1966 Volume 39 Issue 11 Pages 2527-2531
    Published: 1966
    Released: March 27, 2006
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    The hydrogenation of aniline in fluidized beds was studied. As a result of the experiments, the following conclusions were obtained: 1) The reaction rate of the catalytic hydrogenation of aniline in the temperature range between 150°C and 180°C was approximately first-order with respect to hydrogen. In the case of a large molar ratio of hydrogen to aniline, however, the reaction rate became zeroth-orcler with respect to aniline. 2) A good agreement was obtained between the conversion by the fluidized-bed experiment and the values calculated on the model of the contact-time distribution for low degrees of conversion. For high degrees of conversion, the deviation of the values calculated using this model from the experimental value was found to be about 10%. It was suggested that this model can well be applied to predicting the conversion for zeroth-order reaction within the limits of uncertainty given above.
  • D. R. Gupta, S. K. Garg
    1966 Volume 39 Issue 11 Pages 2532-2534
    Published: 1966
    Released: March 27, 2006
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  • Yoshio Tazima, Sadao Yuguchi
    1966 Volume 39 Issue 11 Pages 2534-2535
    Published: 1966
    Released: March 27, 2006
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  • Mitsuo Ebata, Yasuo Takahashi, Hideo Otsuka
    1966 Volume 39 Issue 11 Pages 2535-2538
    Published: 1966
    Released: March 27, 2006
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